[MEASURMENT OF HARDNESS]

Hard water:
Hard water is water that has high mineral content (in contrast with "soft
water"). Hard water is formed when water percolates through deposits
of limestone and chalk which
are
largely
made
up
of calcium and magnesium carbonates.
Soft water:
Soft water is surface water that contains low concentrations of ions and in
particular is low in ions of calcium and magnesium. Soft water naturally
occurs where rainfall and the drainage basin of rivers are formed of hard,
impervious and calcium poor rocks

Water's
hardness
is
determined
by
the concentration of multivalent cations in the water. Multivalent cations are
positively charged metal complexes with a charge greater than 1+. Usually,
the cations have the charge of 2+. Common cations found in hard water
include Ca2+ and Mg2+. These ions enter a water supply by leaching from
minerals
within
an aquifer.
Common calcium-containing
minerals
are calcite and gypsum. A common magnesium mineral is dolomite (which
also contains calcium). Rainwater and distilled water are soft, because they
contain few ions.
The following equilibrium reaction describes the dissolving and formation
of calcium carbonate :
CaCO3 + CO2 + CO2

Ca2+ + 2HCO3

The reaction can go in either direction. Rain containing dissolved carbon

dioxide can react with calcium carbonate and carry calcium ions away with it.
The calcium carbonate may be re-deposited as calcite as the carbon dioxide
is lost to atmosphere, sometimes forming stalactites and stalagmites.
Areas with complex geology can produce varying degrees of hardness of
water over short distances.
Types of Hardness:
Basically there are two types of water hardness. Which are given below:
1- Temporary Hardness
2- Permanent Hardness
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[MEASURMENT OF HARDNESS]

Temporary Hardness:
Temporary hardness is a type of water hardness caused by the presence
of dissolved bicarbonate minerals (calcium
bicarbonate and magnesium
bicarbonate). When dissolved, these minerals yield calcium and
magnesium cations (Ca2+,
Mg2+)
and
carbonate
2

and bicarbonate anions (CO3 , HCO3 ). The presence of the metal cations
makes the water hard. However, unlike the permanent hardness caused
by sulphate and chloride compounds.
Mg(HCO3)2

Mg+2 +2HCO3-1

Ca(HCO3)2

Ca+2 + 2HCO3-1

This temporary hardness can be reduced either by boiling the water, or by

the addition of lime (calcium hydroxide) through the softening process
of lime softening. Boiling promotes the formation of carbonate from the
bicarbonate and precipitates calcium carbonate out of solution, leaving water
that is softer upon cooling.
Permanent Hardness:
Permanent hardness is hardness (mineral content) that cannot be removed
by boiling. When this is the case, it is usually caused by the presence
of calcium sulphate and/or magnesium sulphates in the water, which do not
precipitate out as the temperature increases. Ions causing permanent
hardness of water can be removed using a water softener, or ion exchange
column.
Total Permanent Hardness = Calcium Hardness + Magnesium Hardness
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[MEASURMENT OF HARDNESS]
The calcium and magnesium hardness is the concentration of calcium and
magnesium ions expressed as equivalent of calcium carbonate.

Ca+2 + 2Cl-1

CaCl2
MgSO4

Mg+2 + SO4-2

Total permanent water hardness expressed as equivalent of CaCO 3 can be

calculated with the following formula:
Total Permanent Hardness (CaCO3) = 2.5(Ca2+) + 4.1(Mg2+).

Effects of Hard Water:

Domestic:

Soap scum in sinks and bathtubs

Bathtub rings

Spots on dishes or shower doors

Reduced foaming and cleaning abilities of soaps and detergents

Dingy and yellowed clothes with soapy residues that require extra
rinsing to remove

Industrial:

Clogged pipes from buildup of minerals

Increased water heating costs from buildup of minerals, reducing

efficiency of water heaters

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[MEASURMENT OF HARDNESS]
Health Concern:
Calcium and magnesium ions are required for normal metabolism in many
organisms including mammals. The lack of these ions in soft water have
given rise to concerns about the possible health impacts of drinking soft
water, but when used for drinking for long period can lead to stomach
disorders. Especially hard water contains magnesium sulphate can weaken
the stomach permanently.

Possible skin infections from bacteria trapped in pores underneath soap

scum.
Also it leads to hair fall.

Classification:
Following are the limits through we can observe the extent of hardness.

Classification
soft
Slightly hard
Moderately hard
Hard
Very hard

Mg/L
0-17.1
17.1-60
60-120
120-180
More than 180

How we can measure the hardness in water:

Hardness can be quantified by instrumental analysis. The total water
hardness is the sum of the molar concentrations of Ca2+ and Mg2+, in mol/L or
mmol/L units. Although water hardness usually measures only the total
concentrations
of
calcium
and
magnesium
(the
two
most
prevalent divalent metal ions), iron, aluminium, and manganese can also be
present at elevated levels in some locations. The presence of iron
characteristically confers a brownish (rust-like) color to the calcification,
instead of white (the color of most of the other compounds).
Most commonly we use to measure the hardness by titration with an EDTA
solution. In this titration we use to add small amount of a solution to a water
sample (whose hardness is to be measured) until the color of sample
changes. Then we use to titrate a sample for total hardness using a
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[MEASURMENT OF HARDNESS]
burette .we can also measure hardness separately from magnesium ions and
also from calcium ions by adjusting the pH and using different type of
indicators.
Proper experiment is given below:
Apparatus used:

Distilled water
Tripod stand
Burette
Titration flask
Pipette
Stand

Reagents used:

0.01M EDTA
Buffer solution of ammonium chloride and ammonium hydroxide
(NH4Cl+NH4OH) for total hardness
Buffer solution of sodium chloride and sodium hydroxide (NaCl+NaOH)
for calcium and magnesium hardness.
EBT or EBBR as indicator.

Chemical reactions involved:

M+2

M + 2EBT complex (wine red)

M + 2EBT complex + EDTA

M +2EDTA + EBT

Procedure:

Total Hardness:

We took 50 ml water in titration flask.

Then we added 1-2 of buffer solution in that flask to maintain the pH in
control.
Then we added little amount of EBT indicator.
The color of the solution suddenly changed into wine red.
Before starting the titration process, we noted the initial reading of
burette.

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[MEASURMENT OF HARDNESS]

Then we titrated this solution against standard solution of EDTA

solution of molarity 0.01 mg/L until the color of solution changed into
blue color.
After the color changed, we stopped adding EDTA solution and noted
the burette reading.
We performed that experiment 3 times to minimize the error by taking
the mean value.

Calcium Hardness:

I took 50 ml of water sample in a titration flask.

I added 1-2 ml buffer solution of NaCl + NaOH to maintain pH.
I added small amount of EBBR indicator. The color of solution
to pink.
I noted the initial reading of burette.
Then i titrated that solution against standard solution of
molarity 0.01 mg/L.
The color of solution became purple or dark blue, then i
adding EDTA solution and noted the reading of burette.
I repeated the same procedure three times to minimize the
taking the average value

changed

EDTA of
stopped
error by

Calculations

For blank sample:

Initial

reading Final

reading Vol.

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used

of
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[MEASURMENT OF HARDNESS]
Sample No
1
2
3

Mean

vol.

of Burette
16.5
17.3
18.2

of burette
17.3
18.2
18.9

used

of

titrant

titrant (ml)
0.8
0.6
0.7
0.8+0.6+0.7
3

V = 0.7 ml
Hardness of blank sample =

V molarity of titrant M .W of CaCO 3 1000

vol . of sample ml
0.7 0.01 100 1000
50

= 14mg/L as CaCO3

For water samples,

Sample
1
2
3

Initial
reading
0
2.9
17.3

Final
reading
13.6
19.5
39

Vol. used of titrant

(ml)
13.6
16.6
21.7

Mean vol. of titrant used for water sample, A =

13.6+ 16.6+21.7
3

B = 17.3 ml
Harness of water samples are calculated from the following formula,
Harness as CaCO3 =

( AB)molarity of titrant M . W of CaCO 3 1000

vol . of sampleml

Total Hardness of water sample =

( 17.30.7 ) 0.01 100 1000

50

= 332 mg/L as CaCO 3

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[MEASURMENT OF HARDNESS]
For Calcium Hardness;

S. No
1.
2.
3.

Initial
reading
0
17
26.4

Final
reading
16.7
26.4
38

Volume used of titrant

(ml)
16.7
9.5
11.7

Mean vol. of titrant used for water sample, V =

16.7+ 9.5+11.7
3

B = 12.63 ml
Calcium Harness of water samples is calculated from the following
formula,
Calcium
Harness
of
V molarity of titrant M .W of Calcium 1000
vol .of sampleml
Calcium Hardness of water sample =

water

sample

12.63 0.01 4 0 1000

50

= 101.04 mg/L as CaCO 3

For Magnesium Hardness;

Magnesium Hardness of water sample = Total Hardness
Hardness

Calcium

= 332 101.04
= 230.96 mg/L as CaCO3

Precautions:

Make sure to use lab coats and other safety equipment, while
performing the experiment in the lab.
Take care of using the proper indicator and buffer solution.
Take the volume of chemicals carefully.

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[MEASURMENT OF HARDNESS]

Calculations must be done with proper care and also note the readings
carefully.

Comments:
After performing the experiment and while looking at the results, it is clearly
noticed that distilled water (soft water) has hardness of 14 mg/L as CaCO 3.
And sample water has total harness of 332 mg/L as CaCO 3. Calcium hardness
contributing 101.04 mg/L in total hardness. By subtracting the calcium
hardness from total hardness, we calculated the magnesium hardness which
is 230.96 mg/L as CaCO3. So we observed that sample water has more
hardness due to magnesium contribution in sample water as compared to
calcium.

Department of Environmental Engineering, UET TAXILA

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